title: Dihydropyranone formation by ipso C-H activation in a glucal 3-carbamate-derived rhodium acyl nitrenoid.
abstract: By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C-H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway because of the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene.
authors.affiliation: Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA.
authors.forename: Brisa
authors.initials: B
authors.lastname: Hurlocker
authors.forename: Nadia C
authors.initials: NC
authors.lastname: Abascal
authors.forename: Lindsay M
authors.initials: LM
authors.lastname: Repka
authors.forename: Elsy
authors.initials: E
authors.lastname: Santizo-Deleon
authors.forename: Abigail L
authors.initials: AL
authors.lastname: Smenton
authors.forename: Victoria
authors.initials: V
authors.lastname: Baranov
authors.forename: Ritu
authors.initials: R
authors.lastname: Gupta
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Bernard
authors.forename: Shenjuti
authors.initials: S
authors.lastname: Chowdhury
authors.forename: Christian M
authors.initials: CM
authors.lastname: Rojas
mesh_terms: D002125:Calcium Gluconate / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry; D002384:Catalysis; D006860:Hydrogen Bonding; D007700:Kinetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D011188:Potassium / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D014105:Tosyl Compounds / Q000737:chemistry*
chemical_list: C561207:(N-tosyloxy)-3-O-carbamoyl-D-glucal; D002219:Carbamates; D002254:Carbonates; D009942:Organometallic Compounds; D016877:Oxidants; D014105:Tosyl Compounds; C037593:potassium carbonate; D012238:Rhodium; D011188:Potassium; D002125:Calcium Gluconate